JP5935416B2 - Dye salt - Google Patents

Description

  The present invention relates to salts useful as dyes.

Conventionally, a dye of a metal complex salt compound has been used for color display using reflected light or transmitted light in various fields (for example, fiber materials, liquid crystal display devices, etc.). Examples of such a dye include C.I. represented by the following formula, which is a chromium complex dye having an azo compound as a ligand. I. Solvent Yellow 21 is widely known.

Industrial Dies Chemistry, Properties, Applications, WILEY-VCH, 2003.

  The above-described C.I. I. In some cases, the spectral density of Solvent Yellow 21 was not always satisfactory.

［式（０）中、Ｒ^１は、炭素数１〜８の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、−ＯＲ⁸、−ＣＯＯＲ⁸、−ＯＣＯＲ⁸、−ＣＯＮＲ⁸Ｒ^９、炭素数６〜１０の１価の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該飽和炭化水素基に含まれる−ＣＨ_２−は、−ＣＯ−に置き換わっていてもよい。
Ｒ^２は、水素原子、−ＣＮ、又は−ＣＯＮＨ_２を表す。
Ｒ^３は、ハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基を表す。
Ｒ^４〜Ｒ^７はそれぞれ独立に、−Ｒ^８、−ＯＲ^８、−ＣＯＯＲ^８、−ＣＯＲ^８、−ＯＣＯＯＲ^８、−ＯＣＯＲ^８、−ＣＮ、−ＮＯ_２、ハロゲン原子、−ＳＯ_３Ｈ、−ＳＯ_３Ｎａ、−ＳＯ_３Ｋ、−ＳＯ_２ＮＲ^８Ｒ^９又は−ＮＲ^１１Ｒ^１２を表すか、Ｒ^４及びＲ^５、Ｒ^５及びＲ^６並びにＲ^６及びＲ^７は、互いに結合してベンゼン環の炭素を含んだ６〜７員環を形成する。
Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、炭素数１〜８の１価の脂肪族炭化水素基、炭素数７〜１２のアラルキル基、又は炭素数６〜１０の１価の芳香族炭化水素基を表し、該脂肪族炭化水素基、該アラルキル基及び該芳香族炭化水素基に含まれる水素原子は、−ＯＲ^１０で置換されていてもよい。
Ｒ^１０は、水素原子、炭素数１〜８の１価の飽和炭化水素基又は炭素数６〜１０の１価の芳香族炭化水素基を表す。
Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、炭素数１〜８の１価の脂肪族炭化水素基、炭素数２〜８のアシル基又はテトラヒドロフルフリル基を表すか、Ｒ^１１及びＲ^１２は、互いに結合して窒素原子を含んだ環を形成する。
環Ｚ^１及び環Ｚ^２は、互いに独立に、置換基を有していてもよい芳香環を表し、Ｒ^２１及びＲ^２２は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表し、Ｒ^２３及びＲ^２４は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表すか、Ｒ^２３とＲ^２４が一緒になってアルカンジイル基を形成する。Ｒ^２５及びＲ^２６は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表すか、Ｒ^２５とＲ^２６が一緒になってアルカンジイル基を形成する。Ｒ^２７及びＲ^２８は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表すか、Ｒ^２７とＲ^２８が一緒になってアルカンジイル基を形成する。Ｘ^１は、水素原子又は塩素原子を表す。］
［２］Ｒ^４〜Ｒ^７が、互いに独立に、−Ｒ^８、−ＯＲ^８、−ＣＯＯＲ^８、−ＣＮ、−ＮＯ_２、ハロゲン原子、−ＳＯ_３Ｈ、−ＳＯ_３Ｎａ、−ＳＯ_３Ｋ、−ＳＯ_２ＮＲ^８Ｒ^９又は−ＮＲ^１１Ｒ^１２である［１］記載の塩。
［３］Ｒ^１が、−ＯＨで置換されていてもよい炭素数１〜８の１価の飽和炭化水素基又は−ＯＣＯＲ^８で置換されていてもよい炭素数１〜８の１価の飽和炭化水素基である［１］又は［２］記載の塩。
［４］Ｒ^４〜Ｒ^７のうち少なくとも３つが水素原子である［１］〜［３］のいずれか記載の塩。
［５］Ｒ^２が、−ＣＮである［１］〜［４］のいずれか記載の塩。
［６］Ｒ^２３〜Ｒ^２６が、互いに独立に、炭素数１〜８の１価の脂肪族炭化水素基である［１］〜［５］のいずれか記載の塩。
［７］Ｒ^２１及びＲ^２２が、メチル基である［１］〜［６］のいずれか記載の塩。
［８］Ｚ^１およびＺ^２が、メチル基で置換されてもよいベンゼン環である［１］〜［７］のいずれか記載の塩。
［９］［１］〜［８］のいずれか記載の塩を有効成分とする染料。
［１０］［９］記載の染料、樹脂及び溶剤を含む着色樹脂組成物。 The present invention provides the following [1] to [10].
[1] A salt represented by the formula (0).

[In the formula (0), R ¹ represents a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is —OR ⁸ , —COOR ⁸ , —OCOR ^8. , -CONR ⁸ R ⁹ , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group may be substituted with —CO—. It may be replaced.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4 to} R ⁷ are each independently —R ⁸ , —OR ⁸ , —COOR ⁸ , —COR ⁸ , —OCOOR ⁸ , —OCOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, — _{SO 3 Na, -SO 3 K,} -SO 2 NR 8 R 9 or ^-NR 11 or represents ^{R 12, R 4} and ^R 5, ^{R 5} and ^{R 6} and ^{R 6} and ^{R 7,} benzene combined with each other A 6-7 membered ring containing the ring carbon is formed.
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -OR ¹⁰ .
R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ¹¹ and R ¹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group, or R ¹¹ and R 12 ¹² combine with each other to form a ring containing a nitrogen atom.
Ring Z ¹ and Ring Z ² each independently represent an optionally substituted aromatic ring, and R ²¹ and R ²² each independently represent a substituent having 1 to 1 carbon atoms. 12 represents an aliphatic hydrocarbon group or a hydrogen atom having 12 carbon atoms, and R ²³ and R ²⁴ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ²³ and R ²⁴ together form an alkanediyl group. R ²⁵ and R ²⁶ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, or R ²⁵ and R ²⁶ together represent an alkanediyl group. Form. R ²⁷ and R ²⁸ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, or R ²⁷ and R ²⁸ together form an alkanediyl group. Form. X ¹ represents a hydrogen atom or a chlorine atom. ]
[2] R ^{4 to} R ⁷ are independently of each other —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K. a _-SO 2 ^NR 8 ^{R 9} or ^-NR 11 ^{R 12} [1] salt according.
[3] R ¹ is a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted with —OH, or monovalent saturated group having 1 to 8 carbon atoms which may be substituted with —OCOR ^8. The salt according to [1] or [2], which is a hydrocarbon group.
[4] The salt according to any one of [1] to [3], wherein at least three of R ^{4 to} R ⁷ are hydrogen atoms.
[5] The salt according to any one of [1] to [4], wherein R ² is —CN.
[6] The salt according to any one of [1] to [5], wherein R ^{23 to} R ²⁶ are each independently a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
[7] The salt according to any one of [1] to [6], wherein R ²¹ and R ²² are methyl groups.
[8] The salt according to any one of [1] to [7], wherein Z ¹ and Z ² are benzene rings which may be substituted with a methyl group.
[9] A dye comprising the salt according to any one of [1] to [8] as an active ingredient.
[10] A colored resin composition comprising the dye, resin and solvent according to [9].

  The salt according to the present invention exhibits good spectral density.

The salt of the present invention comprises an anion represented by the following formula (A1) (hereinafter sometimes referred to as “anion (A1)”) and a cation represented by the following formula (A2) (hereinafter referred to as “cation (A2)”). A salt (hereinafter sometimes referred to as “salt (0)”).
R ^{4 to} R ⁷ in the salt (0) are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO _{3 K,} is preferably -SO 2 ^NR 8 ^{R 9} or ^-NR 11 ^{R 12.}
In addition, tautomers of the salts of the present invention are also included in the present invention.

  The anion (A1) can be selected according to the color of the target color filter. It is preferable that the salt containing an anion (A1) is sufficiently dissolved in a solvent. Furthermore, the anion (A1) is preferably dissolved in a developer used for pattern formation to such an extent that the pattern can be formed.

In the anion (A1), examples of the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms in R ¹ and R ¹⁰ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Linear saturated hydrocarbon groups such as n-hexyl group, n-heptyl group, n-octyl group;
Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl Group, 1- (1-methylethyl) butyl group, 1- (1-methylethyl) -2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group Group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1- (1-methylethyl) pentyl group, 1-butylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl-3 -Methylbutyl group, 1- (1,1-dimethylethyl) butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3- Dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4- Dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethyl Rupentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1, 1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3- Dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl Group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1 -Propyl-3-methylbutyl group, 1- (1-methylethyl) -1-methylbutyl group, 1- (1-methylethyl) -2-methylbutyl group, 1- (1-methylethyl) -3-methylbutyl group, Branched saturated hydrocarbon groups such as 1,1-diethylbutyl group and 1,2-diethylbutyl group;
Examples thereof include cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.

In the anion (A1), examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ⁸ and R ⁹ include the groups exemplified above for the linear saturated hydrocarbon group and the branched saturated hydrocarbon group. In addition, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a 2-methylpropenyl group, and the like can be given.
Examples of the aralkyl group having 7 to 12 carbon atoms in R ⁸ and R ⁹ include benzyl group, phenylethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, diphenylmethyl group and the like.
Examples of the monovalent aromatic hydrocarbon group having 6 to ¹⁰ carbon atoms in R ⁸ , R ⁹ and R ¹⁰ include phenyl group, toluyl group, xylyl group, naphthyl group, biphenyl group, fluorenyl group and anthryl group. .

Examples of the saturated hydrocarbon group in which —CH ₂ — is replaced by —CO— include, for example, an acetyl group, a 3-oxobutyl group, a 2-oxobutyl group, a 3-oxopentyl group, a 2-oxopentyl group, and a 3-oxohexyl group. An oxo group-containing saturated hydrocarbon group such as
Phenacyl group, 2-oxo-2-naphthylethyl group, 2-oxo-2-hydroxyphenylethyl group, 2-oxo-2-hydroxynaphthylethyl group, 2-oxo-2-methoxyphenylethyl group, 2-oxo- Examples include 2-methoxynaphthylethyl group, 2-oxo-3-phenylpropyl group, 2-oxo-3-naphthylpropyl group aromatic hydrocarbon group and oxo group-containing saturated hydrocarbon group.

  Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a fluoromethyl group, a fluoropropyl group, a fluorobutyl group, a chloromethyl group, a chloroethyl group, and a chloropropyl group. Chlorobutyl group, bromomethyl group, bromoethyl group, bromopropyl group, bromobutyl group, iodomethyl group, iodoethyl group, iodopropyl group, iodobutyl group and the like.

As —OR ⁸ , for example, hydroxy group, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, phenoxy group, benzyloxy Group, benzoyloxy group and the like.
Examples of —OR ⁸ substituted with —OR ¹⁰ include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, 1-ethoxypropyl group, 2-ethoxypropyl group, 1- Ethoxy-1-methylethyl group, 1-methyl-2-ethoxyethyl group, 1- (1-methylethoxy) propyl group, 2- (1-methylethoxy) propyl group, 1- (1-methylethoxy) -1 -Methylethyl group, 2- (1-methylethoxy) -1-methylethyl group, 3-ethoxypropyl group and the like can be mentioned.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with —OR ⁸ include, for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxymethoxymethyl group, a 2-hydroxyethoxymethyl group, 2- Hydroxy group-containing saturated hydrocarbon groups such as hydroxymethoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2-oxo-4-hydroxybutyl group;
Contains alkoxy groups such as methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, 2-oxo-4-methoxybutyl group Saturated hydrocarbon groups;
Methoxymethoxymethyl group, 2-methoxyethoxymethyl group, ethoxymethoxymethyl group, 2-ethoxyethoxymethyl group, propoxymethoxymethyl group, 2-propoxyethoxymethyl group, 2-methoxymethoxyethyl group, 2- (2-methoxyethoxy ) Saturated hydrocarbon groups containing alkoxyalkyl groups such as ethyl group, 2-ethoxymethoxyethyl group, 2- (2-ethoxyethoxy) ethyl group, 2-propoxymethoxyethyl group, 2- (2-propoxyethoxy) ethyl group;
Phenyloxymethyl group, 1-naphthyloxymethyl group, 2-naphthyloxymethyl group, hydroxyphenyloxymethyl group, hydroxynaphthyloxymethyl group, methoxyphenyloxymethyl group, methoxynaphthyloxymethyl group, 3-phenoxy-2-oxo Aryloxy group-containing saturated hydrocarbon group such as propyl group;
Aralkyloxy groups such as benzyloxymethyl group, naphthylmethoxymethyl group, hydroxybenzyloxymethyl group, hydroxynaphthylmethoxymethyl group, methoxybenzyloxymethyl group, methoxynaphthylmethoxymethyl group, phenyloxyethoxymethyl group, naphthyloxyethoxymethyl group Examples thereof include saturated hydrocarbon groups.

Examples of —COOR ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with —COOR ⁸ include a carboxy group-containing saturated hydrocarbon group such as a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group;
Methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxycarbonylmethyl group, propoxycarbonylethyl group, butoxycarbonylmethyl group, butoxycarbonylethyl group, phenoxymethoxycarbonylmethyl group, 2-hydroxyethoxy Alkoxycarbonyl group-containing saturated hydrocarbon group such as carbonylmethyl group, 2-methoxyethoxycarbonylmethyl group, etc .;
Aryloxycarbonyl-containing saturated hydrocarbon groups such as phenoxycarbonylmethyl group and naphthyloxycarbonylmethyl group;
Aralkyloxycarbonyl-containing saturated hydrocarbon groups such as benzyloxycarbonylmethyl group and naphthylmethoxycarbonylmethyl group;
2-oxopropoxycarbonylmethyl group, 2- (2-oxopropoxycarbonyl) ethyl group, 3- (2-oxopropoxycarbonyl) propyl group, 2-oxobutoxycarbonylmethyl group, 2- (2-oxobutoxycarbonyl) ethyl Group, 3- (2-oxobutoxycarbonyl) propyl group, 2-oxopentyloxycarbonylmethyl group, 2- (2-oxopentyloxycarbonyl) ethyl group, 3- (2-oxopentyloxycarbonyl) propyl group, 3 -Oxobutoxycarbonylmethyl group, 2- (3-oxobutoxycarbonyl) ethyl group, 3- (3-oxobutoxycarbonyl) propyl group, 3-oxopentyloxycarbonylmethyl group, 2- (3-oxopentyloxycarbonyl) Ethyl group, 3- (3-oxope It is -CO - chill oxycarbonyl) propyl group, 2-oxo-hexyl oxycarbonyl methyl group, 2- (2-oxo-hexyl oxycarbonyl) ethyl group, 3- (2-oxo-hexyl oxycarbonyl) -CH ₂ and propyl group A saturated hydrocarbon group containing an alkoxycarbonyl group replaced with-;
3-methoxycarbonyl-2-oxopropyl group, 4-methoxycarbonyl-3-oxobutyl group, 5-methoxycarbonyl-4-oxopentyl group, 3-ethoxycarbonyl-2-oxopropyl group, 4-ethoxycarbonyl-3- Oxobutyl group, 5-ethoxycarbonyl-4-oxopentyl group, 3-propoxycarbonyl-2-oxopropyl group, 4-propoxycarbonyl-3-oxobutyl group, 5-propoxycarbonyl-4-oxopentyl group, 4-methoxycarbonyl 2-oxobutyl group, 4-methoxycarbonyl-3-oxopentyl group, 5-methoxycarbonyl-4-oxohexyl group, 4-ethoxycarbonyl-2-oxobutyl group, 4-ethoxycarbonyl-3-oxopentyl group, 5 -Ethoxycarbonyl-4 Oxo-hexyl group, 4-propoxycarbonyl-2-oxobutyl group, 4-propoxycarbonyl-3-oxopentyl group, and a content alkoxycarbonyl groups such as 5-propoxycarbonyl-4-oxo-hexyl group -CH ₂ - is -CO A saturated hydrocarbon group replaced by-; and the like.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with —CONR ⁸ R ⁹ include, for example, N-methylaminocarbonylmethyl group, N-methylaminocarbonylethyl group, N, N-dimethylaminocarbonylmethyl group, N, Alkyl-substituted carbamoyl group-containing saturated hydrocarbon groups such as N-dimethylaminocarbonylethyl group, N, N-ethylmethylaminocarbonylmethyl group, N, N-ethylmethylcarbonylethyl group;
Aryl-substituted carbamoyl group-containing saturated hydrocarbon groups such as N-phenylaminocarbonylmethyl group, N, N-phenylmethylcarbonylmethyl group, N, N-diphenylcarbonylmethyl group, N, N-phenylbenzylcarbonylmethyl group;
Aralkyl group-substituted carbamoyl group-containing saturated hydrocarbon group such as N-benzylaminocarbonylmethyl group, N, N-dibenzylcarbonylmethyl group, N, N-bis (2-phenylethyl) carbonylmethyl group; and the like.

Examples of —OCOR ⁸ include an acetyloxy group, a pivaloyloxy group, and a benzoyloxy group.

Examples of the saturated hydrocarbon group in which the hydrogen atom is substituted with —OCOR ⁸ include acetyloxymethyl group, acetyloxyethyl group, ethylcarbonyloxymethyl group, ethylcarbonyloxyethyl group, propylcarbonyloxymethyl group, propylcarbonyl Oxyethyl, butylcarbonyloxymethyl, butylcarbonyloxyethyl, hexanoyloxyethyl, 2-ethylbutyryloxyethyl, 2-ethylhexanoyloxyethyl, 2-propylhexanoyloxyethyl, Alkylcarbonyloxy group-containing saturated hydrocarbon groups such as valoyloxyethyl group and 2-methylpropionyloxyethyl group;
Benzoyloxymethyl group, benzoyloxyethyl group, naphthyloxycarbonylmethyl group, benzylcarbonyloxymethyl group, naphthylmethylcarbonyloxymethyl group, methylbenzoyloxymethyl group, 2-methylbenzoyloxyethyl group, 4-methylbenzoyloxyethyl group 3,4-dimethylbenzoyloxyethyl group, hydroxybenzoyloxymethyl group, methoxybenzoyloxymethyl group, 4-methoxybenzoyloxyethyl group, 3,4-dimethoxybenzoyloxyethyl group and other aromatic hydrocarbon groups and carbonyloxy And group-containing saturated hydrocarbon groups.

Examples of —COR ⁸ include an acetyl group, a propionyl group, an isobutyryl group, a valeryl group, and an isovaleryl group.
-OCOOR ⁸ includes, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyloxy group, isobutoxycarbonyloxy group, sec-butoxycarbonyloxy group , N-pentyloxycarbonyloxy group, phenoxycarbonyloxy group and the like.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms include a benzyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, and a group represented by the following formula: Etc.

In the anion (A1), R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aliphatic hydrocarbon having 1 to 8 carbon atoms in which a hydrogen atom is substituted with —OR ^8. A monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms in which a hydrogen atom is substituted with —COOR ⁸ , or a monovalent aliphatic group having 1 to 8 carbon atoms in which a hydrogen atom is substituted with —OCOR ⁸ Hydrocarbon groups are preferred, groups represented by formula (f-1) to formula (f-16) are more preferred, and formula (f-1), formula (f-7), formula (f-15) and The groups each represented by formula (f-16) are more preferable. When R ¹ is the above group, the compound of the present invention tends to exhibit high solubility in an organic solvent. In formula (f-1) to formula (f-16), * represents a bonding position with a nitrogen atom on the pyridone ring.

R ² is a hydrogen atom, —CN or —CONH ₂ . Especially, -CN is preferable at the point which is easy to acquire a raw material.

R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an N-butyl group, a sec-butyl group, and a tert-butyl group.
As a C1-C4 alkyl group substituted by the halogen atom, a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned, for example.
R ³ is preferably a methyl group or a trifluoromethyl group, and more preferably a methyl group.

R ^{4 to} R ⁷ are each independently —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K, —SO. is preferably ₂ NR ⁸ R ⁹ or ^{-NR 11 R 12, -R 8,} -OR 8, -COOR 8, -CN, -NO 2, halogen _{atom, -SO 3 H, -SO 3 Na} , - More preferably, it is SO ₃ K or —SO ₂ NR ⁸ R ⁹ . More preferably, at least three of R ^{4 to} R ⁷ are hydrogen atoms. When R ^{4 to} R ⁷ are the above groups, the color density of the salt tends to be high.

Examples of —NR ¹¹ R ¹² in R ^{4 to} R ⁷ include N-methylamino group, N, N-dimethylamino group, N-ethylamino group, N, N-diethylamino group, N-propylamino group, N , N-dipropylamino group, N-butylamino group, N, N-dibutylamino group, N-pentylamino group, N-acetylamino group and the like.
Examples of —NR ¹¹ R ¹² in which R ¹¹ and R ¹² are bonded to each other to form a ring containing a nitrogen atom include a 1-pyrazolyl group, a pyrrolidino group, a piperidino group, and a morpholino group.
Among these, an N-acetylamino group is preferable from the viewpoint of solubility in an organic solvent.

Examples of —SO ₂ NR ⁸ R ⁹ in R ^{4 to} R ⁷ include an unsubstituted sulfamoyl group, an N-1 substituted sulfamoyl group, and an N, N-2 substituted sulfamoyl group.

Examples of the N-1-substituted sulfamoyl group include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, and N-butylsulfamoyl group. N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- ( 2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentyl Rufamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1- Methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group An N-1 substituted sulfamoyl group substituted with an aliphatic hydrocarbon group such as a group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N-allylsulfamoyl group;
N- (2-hydroxyethyl) sulfamoyl group, N- (3-hydroxypropyl) sulfamoyl group, N- (2-hydroxypropyl) sulfamoyl group, N- (2,3-dihydroxypropyl) sulfamoyl group, N- (2 -Hydroxybutyl) sulfamoyl group, N- (4-hydroxybutyl) sulfamoyl group, N-substituted sulfamoyl group substituted with an aliphatic hydrocarbon group having a hydroxy group such as N- (1-hydroxymethylethyl) sulfamoyl group ;
N- (2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N-methoxypropylsulfamoyl group, N-ethoxypropylsulfamoyl group N-propoxypropylsulfamoyl group, N-isopropoxypropylsulfamoyl group, N-hexyloxypropylsulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (3-tert- Butoxypropyl) sulfamoyl group, N- (4,4-dimethoxybutyl) sulfamoyl group, N-substituted sulfamoyl group substituted with an alkyl group or cycloalkyl group having an alkoxy group such as N-methoxyhexylsulfamoyl group;
An N-1 substituted sulfamoyl group substituted with an aliphatic hydrocarbon group having an alkoxyalkyl group such as an N- [1- (2-ethoxyethoxy) propyl] sulfamoyl group;
An N-1-substituted sulfamoyl group substituted with an aryl group such as an N-phenylsulfamoyl group and an N- (1-naphthyl) sulfamoyl group;
N-benzylsulfamoyl group, N- (1-phenylethyl) sulfamoyl group, N- (2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl Group, N- [2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) ethyl] sulfamoyl group, N- (3-phenyl-1-propyl) sulfamoyl group, N- ( N-1-substituted sulfamoyl group substituted with an aralkyl group such as 3-phenyl-1-methylpropyl) sulfamoyl group;
N- (3,4,5-trimethoxybenzyl) sulfamoyl group, N- [2- (3,4-dimethoxyphenyl) ethyl] sulfamoyl group, N- [2- (2-ethoxyphenyl) ethyl] sulfamoyl group, etc. N-1 substituted sulfamoyl group substituted with an aralkyl group having the following substituents;

Examples of the N, N-2 substituted sulfamoyl group include N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, and N, N-propylmethyl. Sulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) ) N, N-substituted sulfamoyl group substituted by two aliphatic hydrocarbon groups such as sulfamoyl group, N, N-heptylmethylsulfamoyl group;
N, N-bis (2-hydroxyethyl) sulfamoyl group, N, N-bis (2-methoxyethyl) sulfamoyl group, aliphatic hydrocarbon having substitution such as N, N-bis (2-ethoxyethyl) sulfamoyl group And N, N-2 substituted sulfamoyl group substituted with a group.

The ^{R 8} and ^{R 9} in the -SO ₂ NR ⁸ R ^9, branched alkyl groups having 6 to 8 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, 2 to 8 carbon atoms A hydroxy group-containing alkyl group or aryl group, or an alkoxy group-containing alkyl group or aryl group having 2 to 8 carbon atoms is preferable, and a 2-ethylhexyl group is more preferable.

  It is preferable that the salt containing a cation (A2) is sufficiently dissolved in a solvent. Furthermore, it is preferable that the salt containing a cation (A2) is dissolved in a developer used for pattern formation described later to such an extent that the pattern can be formed.

  In addition, since the cation (A2) has a resonance structure, a cation in which the charge of the cation described in the formula (A2) is transferred is also included in the present invention.

In the cation (A2), the ring Z ¹ and the ring Z ² each independently represent an aromatic ring which may have a substituent. The aromatic ring is preferably a benzene ring or a naphthalene ring.

Examples of the substituent on the benzene ring and the naphthalene ring include
Aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl;
Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group;
Aryloxy groups such as phenoxy groups;
An aralkyloxy group such as a benzyloxy group;
Acyloxy groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group;
Methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group Alkylsulfamoyl groups such as a famoyl group, n-butylsulfamoyl group, di-n-butylsulfamoyl group;
Alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Examples thereof include a nitro group and a cyano group.
When the substituent has a hydrogen atom, the hydrogen atom is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group. , Isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; aryloxy group such as phenoxy group, benzyloxy group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group An aromatic hydrocarbon group such as a group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group; carboxy group; cyano group; nitro group;

From the viewpoint of solubility, the ring Z ¹ and the ring Z ² are each preferably a benzene ring that may be substituted, and more preferably an unsubstituted benzene ring.

In the cation (A2), X ¹ is preferably a hydrogen atom.

In the cation (A2), when R ²¹ and R ²² are an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, the aliphatic hydrocarbon group includes, for example, a methyl group, Ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group, hexyl group, Examples include isohexyl group, 5-methylhexyl group, heptyl group, and octyl group.
Examples of the substituent in the aliphatic hydrocarbon group include:
Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Examples thereof include alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and benzyloxy group.
Halogen groups such as fluoro, chloro, bromo and iodo groups;
Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.

In the cation (A2), R ²¹ and R ²² are each independently an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and preferably has a substituent. An aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms having no substituent, and further preferably an n-butyl group. R ²¹ and R ²² are preferably the same group. When R ²¹ and R ²² are the same group, the molar extinction coefficient tends to be better.

In the cation (A2), when R ^{23 to} R ²⁸ are an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, the aliphatic hydrocarbon group is, for example, Methyl, ethyl, vinyl, ethynyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, 2-propynyl, butyl, isobutyl, sec-butyl, tert- Butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-penten-4-ynyl group, Examples include hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, and octyl group.
Examples of the substituent in the aliphatic hydrocarbon group include:
Examples thereof include alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and benzyloxy group.
Halogen groups such as fluoro, chloro, bromo and iodo groups;
Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.
Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, A hexane-1,6-diyl group is mentioned.

In the cation (A2), when R ^{23 to} R ²⁸ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, preferably has a substituent. An alkyl group having 1 to 3 carbon atoms, more preferably a methyl group which may have a substituent, and still more preferably a methyl group having no substituent. R ²³ and R ²⁴ , R ²⁵ and R ²⁶ , R ²⁷ and R ²⁸ are preferably the same group.

In the cation (A2), when R ²³ and R ²⁴ together form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms. More preferably a pentane-1,5-diyl group.

In the cation (A2), when R ²⁵ and R ²⁶ together form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms. More preferably a pentane-1,5-diyl group.

  Examples of the hydrocarbon ring formed from the alkanediyl group include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. The hydrocarbon ring may have a substituent, and specific examples of the substituent include an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. be able to.

In the cation (A2), when R ²⁷ and R ²⁸ together form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 3 to 5 carbon atoms. More preferably a propane-1,5-diyl group.

  Examples of the hydrocarbon ring formed from the alkanediyl group include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, and a cycloheptene ring. The hydrocarbon ring may have a substituent, and specific examples of the substituent include an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. be able to.

  In the compound (0), the cation (A2) is preferably a cation represented by the formulas (II-1) to (II-36).

Examples of the salt (0) include a salt (I-1) to a salt (I-300). A ⁺ represents a cation (A2). In Table 1, the column A ⁺ indicates the number of the cation formula exemplified above. ⁿ Bu represents an n-butyl group, and Et represents an ethyl group. Moreover, when the formula number is described in the R ¹ column, the formula number of the group shown above is described.

［式中、
Ｒ^１−Ａは、炭素数１〜３の１価の飽和炭化水素基、水酸基で置換された炭素数１〜３の１価の飽和炭化水素基、又は−ＯＣＯＲ^８−Ａで置換された炭素数１〜３の１価の飽和炭化水素基（ここでＲ^８−Ａは炭素数１〜８の１価の脂肪族炭化水素基を表す。）を表し、
Ｒ^５−Ａは、水素原子、−ＯＲ^８−B (ここでＲ^８−Bは炭素数１〜８の１価の脂肪族炭化水素基を表す。)、又は−ＮＨＲ^１１−Ａ(ここでＲ^１１−Aは炭素数１〜８の１価の脂肪族炭化水素基を表す。)を表し、
Ｒ^６−Ａは、水素原子、又は−ＯＲ^８−B (ここでＲ^８−Bは炭素数１〜８の１価の脂肪族炭化水素基を表す。)を表し、
Ｒ^２１−Ａは、炭素数１〜４の１価の飽和炭化水素基を表し、
Ｒ^２２−Ａは、炭素数１〜４の１価の飽和炭化水素基を表し、
Ｒ^{１００−Ａ}は、水素原子、又はメチル基を表す。］
塩（Ｉ−１）、塩（Ｉ−２）、塩（Ｉ−２８６）および塩（Ｉ−２９９）が、分光濃度が特に高く、好ましい。 As an aspect of the salt of this invention, the following are mentioned, for example.
A compound represented by formula (0-A).

[Where:
R ^1-A is a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms, a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms substituted with a hydroxyl group, or carbon substituted with —OCOR ^8-A. A monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (wherein R ^{8 -A} represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms),
R5 ^-A is a hydrogen atom, -OR8 ^-B (wherein R8 ^-B represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms), or -NHR11 ^-A (wherein R ^11-A represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms).
R6 ^-A represents a hydrogen atom or -OR8 ^-B (wherein R8 ^-B represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms);
R ^21-A represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms,
R ^22-A represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms,
R ^100-A represents a hydrogen atom or a methyl group. ]
The salt (I-1), the salt (I-2), the salt (I-286) and the salt (I-299) are particularly preferable because of their particularly high spectral density.

  A method for producing the salt (0) of the present invention will be described.

  The salt (0) is formed by using a compound represented by the formula (d) (hereinafter sometimes referred to as “compound (d)”) and a chromium compound to form a salt containing the anion (A1), It can manufacture by carrying out the salt exchange reaction of the salt containing A1) and the salt containing a cation (A2).

［式（ｄ）中、Ｒ^１〜Ｒ^７は、式（０）におけるものと同じ意味を表す。］

[In formula (d), R ^{1 to} R ⁷ represent the same meaning as in formula (0). ]

As a method for producing the compound (d), it can be produced, for example, by the method described in JP-B-7-88633, that is, by diazo coupling a diazonium salt and a pyridone compound.
Specifically, the compound (d) can be produced by diazo coupling a diazonium salt represented by the formula (b) and a pyridone compound represented by the formula (c). The diazonium salt represented by the formula (b) can be obtained, for example, by diazotizing the amine represented by the formula (a) with nitrous acid, nitrite or nitrite.

[In formula (a), formula (b) and formula (c), R ^{1 to} R ⁷ represent the same meaning as in formula (0). A ¹ represents an inorganic anion or an organic anion. ]

Examples of the inorganic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, and the like. Examples of the organic anion include CH ₃ —COO ⁻ and C ₆ H ₅ —COO ^— . Preferred are chloride ion, bromide ion and CH ₃ —COO ^— .

  Compound (d) can be produced by reacting the diazonium salt represented by formula (b) with the pyridone compound represented by formula (c) in an aqueous solvent. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

  The method for obtaining the target compound (d) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, the reaction mixture can be mixed with an acid (such as acetic acid) and water, and the precipitated crystals can be collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is usually from 10 ° C to 50 ° C, preferably from 20 ° C to 50 ° C, preferably from 20 ° C to 30 ° C. Moreover, after adding a reaction mixture to the aqueous solution of an acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The salt containing an anion (A1) is obtained by combining the compound (d) and the chromium compound in an aqueous solvent (for example, N, N-dimethylformamide, N-methylpyrrolidone, etc.), preferably at 70 to 150 ° C. and 3 to 10 It can manufacture by making it react for time.

Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, chromium fluoride, ammonium sulfate chromium, and preferably chromium formate, ammonium sulfate, and the like.
It is preferable that the usage-amount of a chromium compound is 0.5-1 mol with respect to 1 mol of compounds (d).

  In order to promote the reaction, an inorganic base can be present together.

  Examples of the inorganic base include sodium hydroxide, calcium hydroxide, sodium carbonate, calcium carbonate, sodium acetate, calcium acetate and the like, preferably sodium carbonate and sodium acetate.

  Next, the manufacturing method of salt (0) is demonstrated. The salt (0) can be produced by subjecting a salt containing an anion (A1) and a salt containing a cation (A2) to a salt exchange reaction in a solvent. It is preferable to react the salt containing the anion (A1) represented by the following formula (II ′) and the salt containing the cation (A2) at a molar ratio of 1: 1 to 1: 4.

[In formula (II ′), R ^{21 to} R ² represent the same meaning as described above. A ¹ represents an inorganic anion or an organic anion. ]
A ¹ is preferably a halide ion such as fluoride ion, chloride ion or bromide ion.

  The method for obtaining the target compound salt (0) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with an inorganic salt (eg, sodium chloride) and water, and the precipitated crystals can be collected by filtration. The inorganic salt is preferably prepared by preparing an aqueous solution of an inorganic salt in advance and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 10 ° C. or higher and 40 ° C. or lower, and further preferably 10 ° C. or higher and 25 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an inorganic salt, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The salt of the present invention thus obtained is useful as a dye. In particular, since the spectral density is high, it is useful as a dye for color filters of display devices such as liquid crystal display devices that display colors using reflected light or transmitted light, fiber materials, and the like.

  The dye of the present invention is a dye containing the salt of the present invention as an active ingredient. The content of the salt of the present invention contained in the dye is preferably 3 to 100% by mass, more preferably 10 to 100% by mass.

  The colored resin composition of the present invention contains the dye of the present invention as a colorant (hereinafter sometimes referred to as “colorant (A)”), and further contains a resin (B) and a solvent (E). The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).

In addition to the dye of the present invention, the colorant (A) may further contain a pigment and / or a dye different from the dye of the present invention.
As dyes different from the dyes of the present invention, the Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, reactive, direct And dyes classified as (Direct), Disperse, or Vat. More specifically, dyes having the following color index (CI) numbers can be mentioned, but the dye is not limited thereto.
C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54,76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Green 1,5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

Examples of the pigment include organic pigments and inorganic pigments usually used for pigment dispersion resists. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and other metal compounds. Oxides or mixed metal oxides may be mentioned.
Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment under the Color Index (published by The Society of Dyers and Colorists). More specifically, pigments having the following color index (CI) numbers can be mentioned, but the invention is not limited to these.

C. I. Pigment yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment Green 7, 10, 15, 25, 36, 47 and 58 etc.

The content of the colorant (A) is preferably 5 to 60% by mass with respect to the solid content in the colored resin composition. Here, solid content means the sum total of the component except a solvent in a colored resin composition.
The content of the dye of the present invention contained in the colorant (A) is preferably 3 to 100% by mass.
The dyes and pigments different from the dye of the present invention may be used alone or in combination of two or more with the dye of the present invention.

The resin (B) is not particularly limited, and any resin may be used.
The resin (B) is preferably an alkali-soluble resin, and more preferably a resin containing a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Specific examples of the resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, and the like.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 5,000 to 35,000, and more preferably 6,000 to 30,000.
The acid value of the resin (B) is preferably 50 to 150 mg-KOH / g, more preferably 60 to 135 mg-KOH / g.
Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a colored resin composition, More preferably, it is 13-60 mass%.

  The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical, an acid, or the like generated from the polymerization initiator (D). For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned.

The polymerizable compound (C) is preferably a photopolymerizable compound having 3 or more polymerizable groups. Examples of the photopolymerizable compound having 3 or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Is mentioned. The photopolymerizable compounds (C) may be used alone or in combination of two or more.
It is preferable that content of a polymeric compound (C) is 5-65 mass% with respect to solid content of a colored resin composition, More preferably, it is 10-60 mass%.

As said polymerization initiator (D), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by the action of heat or light. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.
Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Examples include benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine and the like.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.
The polymerization initiators (D) may be used alone or in combination of two or more.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator is within the above range, it is preferable because the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

  Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and cyclopentanone. And cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Chill, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ -Butyrolactone etc. are mentioned.

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Content of the solvent (E) in a colored resin composition becomes like this. Preferably it is 70-95 mass% with respect to a colored resin composition, More preferably, it is 75-90 mass%.

  The colored resin composition of the present invention can be used in various ways such as surfactants, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc. An additive may be included.

The salt of the present invention is useful as a dye. In addition, since the salt of the present invention has high absorbance, the spectral density representing the color density per unit density is high, and is particularly useful as a dye used in a color filter of a display device such as a liquid crystal display device. .
In addition, the colored resin composition containing the salt of the present invention includes various display devices such as a display device (for example, a known liquid crystal display device or an organic EL device) having a color filter as a part of its constituent parts, and a solid-state imaging device. It can be used in a known manner for equipment related to colored images.

Next, the present invention will be described more specifically with reference to examples.
In Examples and Comparative Examples,% and part representing content or amount used are based on mass unless otherwise specified.

  In the following Examples, the structure of the compound is NMR (JMM-ECA-500; manufactured by JEOL Ltd.), mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type) and elemental analysis (VARIO). -EL; (Elemental Co., Ltd.)).

[Example 1]
After adding 170 parts of water to 17.0 parts of anthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.4 parts of sodium hydroxide was added and dissolved. Under ice cooling, 25.5 parts of sodium nitrite was added, and then 79.5 parts of 35% hydrochloric acid was added little by little. Thereafter, the mixture was stirred for 2 hours under ice cooling, and 250 parts of 9% amidosulfuric acid aqueous solution was slowly added to quench excess nitrous acid, followed by stirring for about 10 minutes to obtain a suspension containing a diazonium salt.

Subsequently, 24.1 parts of the compound represented by the formula (c-1) were suspended in 170 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise by a pump over about 30 minutes while maintaining the pH of the suspension at 8.0 to 9.5. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 39.9 parts of the compound represented by the formula (d-1). ^The structure was confirmed by ¹ H-NMR.

Identification of compound represented by formula (d-1)
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 1.08 (3H, t), 2.58 (3H, s), 3.88 (2H, q), 7 .32 (1H, t), 7.58 (1H, td), 7.85 (1H, d), 8.05 (1H, dd), 16.4 (1H, s).

  After adding 200 parts of N-methylpyrrolidone to 10 parts of the compound represented by the formula (d-1) and heating to 80 ° C. to dissolve, 3.7 parts of chromium formate n hydrate was added at 135 ° C. The mixture was stirred for about 2 hours, then the temperature was lowered to 80 ° C., 1.2 parts of sodium carbonate was added, and the mixture was again stirred at 135 ° C. for about 2 hours to obtain a dark orange solution. This solution was poured into 1000 parts of a 1N aqueous hydrochloric acid solution, and the resulting orange solid was filtered, washed twice with 80 parts of water, and then vacuum-dried at 60 ° C. to express the formula (f-1). 7.5 parts of the compound obtained are obtained.

Identification of compound represented by formula (f-1) (mass spectrometry) ionization mode = ESI−: m / z = 700.1 [M−Na ⁺ ] ⁻
Exact Mass: 723.1

２，３，３−トリメチル−３H−インドール(和光純薬工業製) ６３部にヨウ化メチル(和光純薬工業製) ６５部を加えて１４０℃で６時間加熱環流を行った。冷却後、ジエチルエーテル１２０部を加えて生じた沈殿をろ取し、冷アセトンにて洗浄した後、減圧下で乾燥してヨウ化１−メチル−２，３，３−トリメチル−３H−インドリウム１０２部を得た（８６％）。 続いてピリジン４７０部、トリエチルアミン６４部とともにヨウ化１−メチル−２，３，３−トリメチル−３H−インドリウム１００部とオルトギ酸エチル (和光純薬工業製)６４部とを１２０℃で１時間反応させた。冷却後、ジエチルエーテル８００部を徐々に加えることにより得られる沈殿をろ過により得る。この固体をエタノールを用いて再結晶を行った後、６０℃２４時間減圧乾燥することにより、式（ｇ−１）で表される化合物を１４５部得た（９０％）。

65 parts of methyl iodide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 63 parts of 2,3,3-trimethyl-3H-indole (manufactured by Wako Pure Chemical Industries, Ltd.), followed by heating at 140 ° C. for 6 hours. After cooling, 120 parts of diethyl ether was added and the resulting precipitate was collected by filtration, washed with cold acetone, dried under reduced pressure, and 1-methyl-2,3,3-trimethyl-3H-indolium iodide. 102 parts were obtained (86%). Subsequently, 470 parts of pyridine, 64 parts of triethylamine, 100 parts of 1-methyl-2,3,3-trimethyl-3H-indolium iodide and 64 parts of ethyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) at 120 ° C. for 1 hour. Reacted. After cooling, a precipitate obtained by gradually adding 800 parts of diethyl ether is obtained by filtration. The solid was recrystallized from ethanol and then dried under reduced pressure at 60 ° C. for 24 hours to obtain 145 parts of a compound represented by the formula (g-1) (90%).

Identification of compound represented by formula (g-1) (mass spectrometry) ionization mode = ESI +: m / z = 357.3 [M−I ⁻ ] ⁺
Exact Mass: 484.1

  To 34 parts of the compound represented by the formula (f-1), 200 parts of N-methylpyrrolidone was added to prepare a solution (s1). Further, 110 parts of N-methylpyrrolidone was added to 23 parts of the compound represented by the formula (g-1) to prepare a solution (t1). Thereafter, the solution (s1) and the solution (t1) were mixed at room temperature, stirred for about 1 hour, and poured into 1280 parts of water. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 37 parts (yield 72%) of the salt represented by the formula (I-1).

Identification of a salt represented by formula (I-1);
(Elemental analysis) C65.0 H5.2 N12.6 Cr4.6

[Example 2]
After adding 88 parts of water to 5.5 parts of anthranilic acid, 3.2 parts of sodium hydroxide was added to obtain a yellow suspension. Under ice cooling, 8.9 parts of sodium nitrite was added, and then 33.2 parts of 35% hydrochloric acid was added little by little. Thereafter, the mixture was stirred for 3 hours under ice cooling. To quench excess nitrous acid, 100 parts of 9% aqueous amidosulfuric acid solution was slowly added and stirred for about 10 minutes to obtain a suspension containing a diazonium salt.

  On the other hand, 26.0 parts of acetoacetic acid ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 24.4 parts of 2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) The parts were mixed and stirred at 95 ° C. for 24 hours. The reaction solution was cooled to room temperature, added to a mixed solution of 304 parts of water and 35 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of a suction filter and dried to obtain 20.4 parts of a compound represented by the formula (c-2).

Next, 8.5 parts of the compound represented by the formula (c-2) was suspended in 77 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise by a pump over about 1 hour while maintaining the pH of the suspension at 8.0 to 9.5. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 11.2 parts of the compound represented by the formula (d-2). ^The structure was confirmed by ¹ H-NMR.

Identification of compound represented by formula (d-2)
¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.56 (3H, s), 3.52 (2H, t), 3.93 (2H, t), 4 .82 (1H, brs), 7.36 (1H, t) 7.74 (1H, t), 8.02-8.06 (1H, 1H, overlapped), 15.7 (1H, s).

  To 10 parts of the compound represented by the formula (d-2), 100 parts of N, N-dimethylformamide, 7.7 parts of ammonium chromium sulfate and 2.6 parts of sodium acetate were added and stirred at 135 ° C. for about 6 hours. An orange solution was obtained. This solution was poured into 20% brine, and the resulting orange solid was filtered, followed by vacuum drying at 60 ° C. to obtain 18 parts of a compound represented by the formula (f-2).

式（ｇ−１）で表される化合物の合成に用いた２，３，３−トリメチル−３H−インドールの代わりに２，３，３, ５−テトラメチルインドレニンを用いた以外は同様の方法にて以下の式（ｇ−２）で表される化合物を合成した。 Identification (mass spectrometry) ionization mode of compound represented by formula (f-2) = ESI−: m / z = 732.1 [M−Na ⁺ ] ⁻
Exact Mass: 755.1

The same method except that 2,3,3,5-tetramethylindolenine was used instead of 2,3,3-trimethyl-3H-indole used in the synthesis of the compound represented by formula (g-1) A compound represented by the following formula (g-2) was synthesized.

Identification of compound represented by formula (g-2) (mass spectrometry) ionization mode = ESI +: m / z = 385.3 [M−I ⁻ ] ⁺
Exact Mass: 512.2

  The solution (s2) was prepared by adding 100 parts of N-methylpyrrolidone to 12.2 parts of the compound represented by the formula (f-2). Further, 80 parts of methanol was added to 8.1 parts of the compound represented by the formula (g-2) to prepare a solution (t2). Thereafter, the solution (s2) and the solution (t2) were mixed at room temperature, stirred for about 1 hour, and poured into 800 parts of water. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 12.1 parts (yield 66%) of the salt represented by the formula (I-2).

Identification of salt represented by formula (I-2) (elemental analysis) C63.6 H5.1 N12.3 Cr4.6

Example 3
After adding 80 parts of water to 19.4 parts of 5- (N-acetylamino) anthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  Next, 20.4 parts of the compound represented by the formula (c-2) was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 39.1 parts of a compound represented by the formula (d-3).

Next, to 39.9 parts of the compound represented by the formula (d-3), 32.5 parts of an acid chloride represented by the formula (e-1) (manufactured by Wako Pure Chemical Industries, Ltd.) is added. The mixture was stirred in methyl pyrrolidone at 70 ° C. for 3 hours. After completion of the reaction, the reaction mixture was charged in water to obtain 50.1 parts of a compound represented by the formula (d-4). The obtained compound was orange and the maximum absorption wavelength (λmax) was measured in an ethyl lactate solvent to show 459 nm. The structure was confirmed by ¹ H-NMR.
¹ H-NMR: 0.72 (3H, m), 0.75 (3H, m), 1.02 (2H, m), 1.07 (2H, m), 1.23 (2H, m), 1.31 (2H, m), 2.06 (3H , s), 2.11 (1H, m), 4.10 (2H, m), 4.24 (2H, m), 7.88 (1H, m), 7.92 (1H, m), 8.32 (1H, d), 10.26 (1H, s), 15.63 (1H, s).

  To 10.0 parts of the compound represented by the formula (d-4), 150 parts of N, N-dimethylformamide, 7.7 parts of ammonium chromium sulfate and 2.6 parts of sodium acetate were added and stirred at 135 ° C. for about 6 hours. A dark orange solution was obtained. This solution was poured into 20% brine, and the resulting orange solid was filtered, followed by vacuum drying at 60 ° C. to obtain 4.9 parts of a compound represented by the formula (f-3).

Identification of compound represented by formula (f-3) (mass spectrometry) ionization mode = ESI−: m / z = 1098.3 [M−Na ⁺ ] ⁻
Exact Mass: 1121.34

A solution (s3) was prepared by adding 110 parts of N-methylpyrrolidone to 18.9 parts of the compound represented by the formula (f-3). Further, 80 parts of N-methylpyrrolidone was added to 8.8 parts of the cyanine compound represented by the formula (g-1) to prepare a solution (t3). Thereafter, the solution (s3) and the solution (t3) were mixed at room temperature, stirred for about 1 hour, and poured into 1300 parts of water. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 19.8 parts (yield 71%) of the salt represented by the formula (I-286).

Identification of salt represented by formula (I-286) (elemental analysis) C63.8 H6.1 N11.2 Cr3.4

Example 4
32.4 parts of benzoyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 30.0 parts of the compound represented by the formula (d-3), and the mixture was stirred at 70 ° C. for 3 hours in N-methylpyrrolidone. . After completion of the reaction, the reaction mixture was charged in water to obtain 35.8 parts of a compound represented by the formula (d-5). The obtained compound was orange and the maximum absorption wavelength (λmax) was measured in an ethyl lactate solvent to show 459 nm. The structure was confirmed by ¹ H-NMR.
2.70 (3H, s), 2.50 (3H, s), 4.28 (2H, t), 4.44 (2H, t), 7.43 (1H, t), 7.57 (1H, m), 7.89 (1H, m), 7.95 (1H, m), 8.35 (1H, m), 10.27 (1H, s), 15.67 (1H, s).

  Next, 150 parts of N, N-dimethylformamide, 7.7 parts of ammonium chromium sulfate, and 2.6 parts of sodium acetate are added to 9.6 parts of the compound represented by the formula (d-5), and the mixture is about 6 at 135 ° C. Stir for hours to give a dark orange solution. This solution was poured into 20% brine, and the resulting orange solid was filtered, followed by vacuum drying at 60 ° C. to obtain 7.1 parts of a compound represented by the formula (f-4).

  A solution (s4) was prepared by adding 150 parts of N-methylpyrrolidone to 15.1 parts of the compound represented by the formula (f-4). Further, 75 parts of N-methylpyrrolidone was added to 8.1 parts of the compound represented by the formula (g-2) to prepare a solution (t4). Thereafter, the solution (s4) and the solution (t4) were mixed at room temperature, stirred for about 1 hour, and poured into 1250 parts of water. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 15.9 parts (yield: 77%) of the salt represented by the formula (I-299).

Identification of salt represented by formula (I-299) (elemental analysis) C64.4 H4.9 N11.7 Cr3.5

<Measurement of absorbance>
A solution having a concentration of 0.028 g / L was prepared by dissolving 0.35 g of the salt in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to 100 cm ³ . The absorbance at the maximum absorption wavelength (λmax) and the maximum absorption wavelength (λmax) of the solution was measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). It was measured. The results are shown in Table 2.

  In Table 2, compound (R-1) is C.I. I. Solvent Yellow 21 (Oleosol Fast Yellow 2G; manufactured by Taoka Chemical Industry Co., Ltd.).

Example 7
[Preparation of colored photosensitive resin composition]
(A) Colorant: salt (I-1): salt synthesized in Example 1 20 parts (B-1) resin: methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, Acid value 70 mg-KOH / g) 70 parts (C-1) polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 30 parts (D-1) polymerization initiator: benzyldimethyl ketal (Irgacure (registered trademark) 651; manufactured by BASF Japan Ltd.) 15 parts and (E-1) solvent: 680 parts of ethyl lactate are mixed to obtain a colored resin composition.

[Production of color filters]
On the glass, the colored resin composition obtained above is applied by a spin coating method to volatilize volatile components. After cooling, light irradiation is performed using a quartz glass photomask having a pattern and an exposure machine. After light irradiation, development is performed with an aqueous potassium hydroxide solution, and the color filter is obtained by heating to 200 ° C. in an oven.

Example 8
A colored resin composition and a color filter are obtained in the same manner as in Example 7, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-2) synthesized in Example 2.

Example 9
A colored resin composition and a color filter are obtained in the same manner as in Example 7, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-3) synthesized in Example 3.

Example 10
A colored resin composition and a color filter are obtained in the same manner as in Example 7, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-4) synthesized in Example 4.

Example 11
A colored resin composition and a color filter are obtained in the same manner as in Example 7, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-286) synthesized in Example 5.

Example 13
A colored resin composition and a color filter are obtained in the same manner as in Example 7, except that the salt (I-1) synthesized in Example 1 is replaced with the salt (I-299) synthesized in Example 6.

上記の樹脂のポリスチレン換算重量平均分子量の測定については、ＧＰＣ法を用いて、以下の条件で行った。
装置 ；ＨＬＣ−８１２０ＧＰＣ（東ソー（株）製）
カラム ；ＴＳＫ−ＧＥＬＧ２０００ＨＸＬ
カラム温度 ；４０℃
溶媒 ；ＴＨＦ
流速 ；１．０ｍＬ／ｍｉｎ
被検液固形分濃度；０．００１〜０．０１％
注入量 ；５０μＬ
検出器 ；ＲＩ
校正用標準物質 ；ＴＳＫ ＳＴＡＮＤＡＲＤ ＰＯＬＹＳＴＹＲＥＮＥ
Ｆ−４０、Ｆ−４、Ｆ−２８８、Ａ−２５００、Ａ−５００
（東ソー（株）製） <Synthesis of Resin B1 Solution>
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the following formula (b-1) and a formula (b-2) The compound to be mixed is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts and 140 parts of ethyl lactate, and the solution is added at 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask kept warm. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the temperature was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw was 1.3 × 10 ⁴ , the solid content was 33% by mass, and the solution acid value was A resin B1 solution of 34 mg-KOH / g was obtained. Calculated from the above solid content and the solution acid value, the solid content acid value of the resin B1 was 100 mg-KOH / g.

About the measurement of the polystyrene conversion weight average molecular weight of said resin, it carried out on condition of the following using GPC method.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.001 to 0.01%
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)

Example 14
[Preparation of colored photosensitive resin composition]
(A) Colorant: Salt (I-1): Salt synthesized in Example 1 30 parts (B-2) Resin: Resin B1 (in terms of solid content) 40 parts (C-2) Polymerizable compound: Dipentaerythritol Mixture of pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 60 parts (D-2) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanyl) Phenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Japan Ltd.) 12 parts (D-3) Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one (Irgacure (registered trademark) 369; manufactured by BASF Japan Ltd.) 6 parts (D2) Polymerization initiation assistant: 4,4′-bis (diethi Amino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 2 parts (E-2) Solvent: Propylene glycol monomethyl ether acetate 528 parts (E-3) Solvent: Propylene glycol monomethyl ether 69 parts, and (F) Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.09 part is mixed to obtain a colored photosensitive resin composition.

[Production of color filters]
Using the resulting colored photosensitive resin composition, a color filter is obtained in the same manner as in Example 7.

  From the results of Table 2, it can be seen that the salt of the present invention has a high spectral density because of its high absorbance. In addition, the colored resin composition containing the compound has excellent color performance and can produce a high-quality color filter.

  The compounds of the present invention are useful as dyes. Since the salt of the present invention has a high absorbance, the spectral density representing the color density per unit density is high, and is particularly useful as a dye used in a color filter of a display device such as a liquid crystal display device.

Claims (10)

A salt represented by the formula (0).

[In the formula (0), R ¹ represents a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is —OR ⁸ , —COOR ⁸ , —OCOR ^8. , -CONR ⁸ R ⁹ , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group may be substituted with —CO—. It may be replaced.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4 to} R ⁷ are each independently —R ⁸ , —OR ⁸ , —COOR ⁸ , —COR ⁸ , —OCOOR ⁸ , —OCOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, — _{SO 3 Na, -SO 3 K,} -SO 2 NR 8 R 9 or ^-NR 11 or represents ^{R 12, R 4} and ^R 5, ^{R 5} and ^{R 6} and ^{R 6} and ^{R 7,} benzene combined with each other A 6-7 membered ring containing the ring carbon is formed.
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -OR ¹⁰ .
R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ¹¹ and R ¹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group, or R ¹¹ and R 12 ¹² combine with each other to form a ring containing a nitrogen atom.
Ring Z ¹ and Ring Z ² each independently represent an optionally substituted aromatic ring, and R ²¹ and R ²² each independently represent a substituent having 1 to 1 carbon atoms. 12 represents an aliphatic hydrocarbon group or a hydrogen atom having 12 carbon atoms, and R ²³ and R ²⁴ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ²³ and R ²⁴ together form an alkanediyl group. R ²⁵ and R ²⁶ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, or R ²⁵ and R ²⁶ together represent an alkanediyl group. Form. R ²⁷ and R ²⁸ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, or R ²⁷ and R ²⁸ together form an alkanediyl group. Form. X ¹ represents a hydrogen atom or a chlorine atom. ] R ^{4 to} R ⁷ are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K, —SO ₂ NR ⁸ R ⁹ or ^-NR 11 salt according to claim 1 wherein ^{R 12.} R ¹ is a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted with —OH or a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted with —OCOR ^8. The salt according to claim 1 or 2, wherein The salt according to any one of claims 1 to 3, wherein at least three of R ^{4 to} R ⁷ are hydrogen atoms. R ² is, salts according to any one of claims 1 to 4 is -CN. R < ²³ > -R < ²⁶ > is a C1-C8 monovalent | monohydric aliphatic hydrocarbon group mutually independently, The salt in any one of Claims 1-5. R <^21> and R <^22> is a methyl group, The salt in any one of Claims 1-6. The salt according to any one of claims 1 to 7, wherein Z ¹ and Z ² are benzene rings which may be substituted with a methyl group.   A dye comprising the salt according to any one of claims 1 to 8 as an active ingredient.   The coloring resin composition containing the dye of Claim 9, resin, and a solvent.